Thermoelectric devices



Aug. 5, 1958 N. E. LINDl-:NBLAD 2,846,494

' THERMOELECTRIC DEVICES Filed Nov. zo, 1955 P-ryff i THfK/fa- 4 HLMY @u INVENTOR. NILS E- I INDENBLHD ATTO/PMSI p with high'melting.pointyductile materials.:Y

Another.. objectl of the vinve'nti'onfisflto @provides` anj imi;

The lpresent finvention- -frealzettesV to `limproved'. thermo. electric devices. More particularly, the invention Arelates to z improvedfthermoelectrio devices including.v high meltf ingI point iron-aluminum therm'oelectrie alloys.

When two.v wires 'fof `dissirnllarmetals have their ends joined-fasfby brazing so as fto-fformwa continuous loop, ia pair of junctions is established between the respectiveends so' vjoinedtwfI-f now'lzhe,` two junctions, arevatwliferent temcircuit thus formed. This effect is called the-therno. electric fori; Seebeck eect Yand fthe. dev-ice fis-*called a thermocouple-(Many arrangements offthetwo wires are possible: -forrl exar'x1ple,thel electromotive :iforce mayfbe read as a vfunetionFof Ytemperature fby? leaving one end ofeach wire unjoined and connecting them series-wise to yav galvanomet'er. Suehamarrangement isrtermed a thermocouple ythermometer; :A- 1 secondY sjunotion f still 'exists- 'insuch a thermometer and is constituted by the joind'erof each of*` they -freef'edsf'of the. wiresby:l rneans .fof 1 the .galvanometer. .1; Alternatively,v thezoppositeeleot; fthat isa ,tern--l perature inereaseffandV Svdecrease, 'mayibeachieved lat-each oneiof thefrjunctions respectively if-V a -ourrent is-passed through the junctions. Thisvis rtermed'fthe Peltier-felled. :Thermoelect'ric materialsvlferelassied asleither` n-type or, fptypedependinguponv the direction of current o'w; accross` the coldljunction -formd by'fthe Vtherxnoelectric metal Aandnanother metal z whenfg operating --fas'f'a lthermo-n electric? generator -acordingfto-the Seebeckt-electz If the positive f'current directioratfthe Ycoldy junction isf/fromr the thermoelectric metal, then it is termedaf -p-.typeb thermo'electric tmaterlal: Thev present=-irlventin 'relates to an Aimprovedi:thermocouple lncludingian improvedwptype thermoelectric element. The electivenessfof such elements ffisegenerally.. evaluatedfgon thecvoltagey 'output iper Ct differecefintemperature; between theicurrett'ermi;

l United States Patent i 2,846,494 Patented Aug. 5, 1958 2 bodimentof thethermocouple device in' accordance with tlie-i-nstantinvent'ion.

MIn the arttof thermoelectric high temperature measurement it is necessary that the temperature responsive element havefa higher melting point than the temperature tobe measured. It is lalso highly desirable .that the element be'relatively ductile,. so that it may' be drawn o otherwise formed into 'various shapes" and of various thicli'nessessuchas, for example, those of a wire. In ad# dition to theseproperties, the thermoelectric element must be capablefof'producing a useful voltage y(i. e., ofa magnitude large enough to be read on a galvanometer-or Vthe like). Heretofore Vthevbest-known p-typ'e therm'oelectric alloyhaving these'prope'rtiesl was Chromel (80% nickel-f 20%.-chro1'nium). Its E. (,withre'specttocopper)l is'at'best-'a'bout 30.2 microVolts-per C.

Itfhas-beenfound that alloys of iron and-aluminum; in,.-addition` tojbeing` ductileyand fhaving `high-melting points, also haveexceptionallyhigher thermal; F.S than ?prior ;p-typethermoelectric `alloys of the high melting point fductile materiall class. ,-'lhiss especiallyt'rue for iron-aluminum alloys in the range of 15.3 %l to29.7%- by .weight aluminum =(or -atomic ratios `of, 8 atoms of iron to 3-7atomsof aluminum). (In all ofthe "followingfetamples; thegE.- yM-.-F.s recorded wereobtained -by employing. junctions between copper land the-'various 1 thermoelectric alloysfof the invention.) Referringfto'Figure '-1, alloy:combinations of v3 `and 4`atoms ofaluminum to 8-atomsfofrir`on produce/E.' Fis of.10`and l5 microvolts'per.o fC-f, respectively. VAn iron-aluminum alloy range ofS.- -fand 7 -aluminum atoms to 8 iron-atoms gives F.sof-30,35 and 30 microvolts per C., respeetivelypfffhus, fthe preferred iron-aluminum atomic aluminum, ybalance iron.

-Itwas -further found thatlcertain additionsfto. theialloys ofithe invention resulted in'evenlarge'r E. M. F.s per C.

For example,an-addition of upto 20%.molybdenu`m-inf creases thethermal E; lM. yof lthe, preferred iron-aluminum alloy-from -35 to45 'microvoltsper C. An alloy consisting 'of- :4: atoms'iof iron yto 3` latoms of `aluminum containing 5%' byl weight molybdenum has anfE. M. yF.

ofrnicrov'olts per C. Anothery alloy of thesame ironfto-aluminum `ratiorontaining about KA7% by 'weight molybdenumfhasamE. M. F.of 45Ymicrovolts rper fC. Thi'sE-. M. lF. of 45 y-mi'crovolts per C.'-was found to hold goodj-for-:percentage additions of "from 7: to 20%- An objet-.foffthe linventiontiszto; provide an improved,

high Ix'neltif'ng point; zpetype `therinoeleotricelement lhaving a-highei 1E; :Mr: F'. per z WIC. than heretofore@attainable` .fjFigure I is` an elevational l viewl yillustrating@oneR embodiment of a thermocouple device in accordance with.;

the instant invention; and

Figure 3 is an elevational view illustrating another rernmolybdenum..r Additions'of fbetween`20% land 25% mo'-,

Fo'radditions beyond this percentage, the thermalfE..-M.TF.

, will continually drop further and further below values 'oftA usefulness. 'i i i j Y -An evenfmore significant increase in the fthermal, E; Mr F.fis-..noted withan addition of up Vto'2'()% by-weight vanadium.. In the casel of the 4Fe:3Al alloy the E. M. -IF.

obtained' with 21.20% addition of yvanadiuml was-60 micro-- v'oltsper C. ff-Asin thecase offmolybdenum'iadditions,v

increases im the vanadiurn percentage beyond l25% by weight resultlin; fa .tapering oil-of Y-the thermalfl'` M; yF.

YThese alloysKare prepared-by melti'ng af mixture vofI thelltwo-:metals;in--the:.desired proportions. -Thes'e metals "f arepreadilyimixed-iin the.proportionsemployed=and 'the molten :alloysafare cast and :solidified f in suitable Aform.

Thereafter 4the alloyed metals, being ductile, may -berlrawn` additions fof indiumjf( about -5 by Weight). enhances 'the' f melting-:ofthe-metalswithout-ultimately aeotin-g the elec.-

trical characteristics ofthe alloy.

8Fez6A1) is a proportional mixture of the compounds FeAl and FeSAl.l However, the FeAl and FesAl compounds are ferromagnetic, whereas 4Fe:3Al is not. The iron-aluminum alloy containing 4 atoms of iron and 3 atoms of aluminum is apparently not such -a mixture of the compounds FeAl and FeAl but rather is unique in its own right since it has been found not to be ferromagnetic. Innumerable examples of similar occurrences are well known in the art of metallurgy.

A typical 'thermocouple device using a p-type thermoelectric alloy according to the instant invention is shown in Figure 2. The device includes a p-type thermoelectric iron-aluminum alloy element 2, the alloy ratio preferably being 8 atoms of iron to 6 atoms of aluminum. Preferably, the p-type thermoelectric element 2 also includes up to 20% by weight molybdenum or vanadium to achieve a higher E. M. F. as described previously. The n-type thermoelectric element 4 preferably consists of an alloy of gold and nickel. Preferably this n-type thermoelectric alloy consists of 7 atoms of gold for each 5 atoms of nickel, or, percentagewise, 17.5% by weight nickel, balance gold. This novel n-type thermoelectric goldnickel alloy element is more fully described land claimed in a co-pending application for Letters Patent, Serial No. 549,960, led November 30, 1955, concurrently herewith. These elements may be in the form of wires or rods, for example.

As shown in Figure 2, the elements 2 and 4 are silversoldered, brazed or welded to a copper block 6. Alternatively the ends of the elements may be directly joined one to the other by silver-soldering, brazing or welding so as to form a single junction therebetween and the copper block 6 omitted entirely. This embodiment of the invention is shown in Figure 3. As shown in Figure 2, the free ends of the elements 2 and 4 are then silversoldered to copper terminal wires or blocks 8 and 10 respectively. The copper terminals 8 and 10 are then connected to any appropriately calibrated device such as a galvanometer 12. The junctions formed by the elements with the copper block 6 constitute, in the case of thermometry, the sensing element in this embodiment. In the embodiment shown in Figure 3 the sensing element is the point-like junction provided by the direct joinder of the two thermoelectric elements one to the other.

Many arrangements of the thermoelectric elements are possible depending upon the type of temperature measurements to be made. For example, where it is desired to make surface measurements on a planar body, the copper block 6 in the embodiment described in connection with Figure 2 will provide more surface contact than the point-like sensing element of Figure 3. On the other hand, the temperature to be measured by a device employing a copper block as in Figure 2 must be somewhat lower than the melting point of the copper block. This result is avoided in the embodiment shown in Figure 3.

It should be understood that iron-aluminum alloys employed in the present invention, as well as the gold-nickel alloys employed, will contain the usual impurities present in commercial grades of these metals, which impurities yare normally present in the nal alloys. Furthermore in the thermocouple device shown in Figure 2 other suitable n-type thermoelectric elements may be used instead of the preferred alloy. Suitable n-type elements may be selected from alloys of bismuth and tellurium, silver and tellurium, and copper and nickel. EX- amples of such n-type alloys are: 2Bi:3Te, PbzTe; and Ag:T e. These are not all of the ductile or high melting point type.

While some of the iron-aluminum alloys mentioned have relatively low thermal E. M. F.s, these alloys are still extremely useful in thermoelectric thermometry due to their high melting points and ductility. Hence it is desired to include these alloys within the scope of the invention as claimed herein.

What is claimed is:

1. A thermocouple including a positive thermoelectric element consisting essentially of an alloy of iron and aluminum with a ratio of 8 atoms of iron to 3-7 atoms of aluminum.

2. A thermocouple including a positive thermoelectric element consisting essentially of an alloy of iron and aluminum with a ratio of 8 atoms of iron t'o 5-7 atoms of aluminum.

3. A thermocouple having a positive thermoelectric element consisting essentially of an alloy of iron and aluminum with a ratio of 8.atoms of iron to 6 atoms of aluminum.

4. A thermocouple including a positive thermoelectric element consisting essentialy of an alloy of iron and aluminum with a ratio of 8 atoms of iron to 347 atoms of aluminum and including up to 25% by weight of an element selected from the group consisting of vanadium and molybdenum.

5. A thermocouple including a positive thermoelectric element consisting essentially of an alloy of iron and aluminum with a ratio of 8 atoms of iron to 3-7 atoms of aluminum and including up to 25% by weight molybdenum.

6. The invention according to claim 5 wherein said ratio of iron to aluminum is 8 atoms of iron to 6 atoms of aluminum.

7. A thermocouple including a positive thermoelectric element consisting essentially of an alloy of iron and aluminum with a ratio of 8 atoms of iron to 3-7 atoms of aluminum and including up to 25% by weight vanadium.

8. The invention according to claim 7 wherein said ratio of iron to aluminum is 8 atoms of iron to 6 atoms of aluminum.

9. A thermocouple comprising a positive element composed of 'an alloy of iron and aluminum with a ratio of 8 atoms of iron to 3-7 atoms of aluminum, and a negative element composed of an alloy of from 78 to 85.5% by weight gold, balance nickel.

10. The invention according to claim 9 wherein the alloy of which said positive element is composed includes up to 25% by weight of an element selected from the group consisting of molybdenum and vanadium.

11. The invention according to claim 9 wherein said positive element is composed of 8 atoms of iron to 5-7 atoms of aluminum.

12. The invention according to claim 9 wherein said negative element is composed of an alloy of 7 atoms of gold to 5 atoms of nickel.

13. A thermocouple comprising a positive element composed of an alloy of iron and aluminum with Iaratio of References Cited in the le of this patent UNITED STATES PATENTS 1,057,753 Marsh Apr. 1, 1913 1,346,062 Ruder July 6, 1920 1,527,628 Brophy Feb. 24, 1925 1,641,752 Flintermann Sept. 6, 1927 2,330,018 Van Wert Sept. 21, 1943 OTHER REFERENCES International Critical Tables, 1929, vol. 6, p. 216.

Koester and Danno'ehl: Die Aushaertung der Gold- Nickel-Leigier-ungen, Zeitschrift fr Metallkunde, p. 248. 

9. A THERMOCOUPLE COMPRISING A POSITIVE ELEMENT COMPOSED OF AN ALLOY OF IRON AND ALUMINUM WITH A RATIO OF 8 ATOMS OF IRON TO 3-7 ATOMS OF ALUMINUM, AND A NEGATIVE ELEMENT COMPOSED OF AN ALLOY OF FROM 78 TO 85.5% BY WEIGHT GOLD, BALANCE NICKEL. 